1. Field of the Invention
The present invention relates to a method for producing 1-hexene from 1-butene.
2. Description of the Prior Art
Compounds having a terminal double bond (hereinafter referred to as "terminal olefins" or ".alpha.-olefins") are very useful industrially as raw materials for heat-resistant polymers, comonomers for the production of polyolefins, starting materials for detergents and so forth. The terminal olefin 1-hexene is especially valuable for many uses such as dimerization to dodecenes which are suitable for making biodegradable detergents, using it as a feed for the OXO reaction to make relatively linear C.sub.7 alcohols, and as a comonomer in making linear low density polyethylene.
A potential source of 1-hexene is a mixture of n-hexenes which contains 1-hexene, cis and trans 2-hexene, and cis and trans 3-hexene. Unfortunately, however, the amount of 1-hexene in these mixtures is normally very low. For example, thermodynamic equilibration of n-hexenes produces a mixture containing only about 2-4 percent 1-hexene. While it is possible to separate the 1-hexene from the other n-hexenes in these mixtures, due to the very low levels of 1-hexene such a procedure would be uneconomical. Thus, there exists a need for a process by which 1-hexene can be made economically and in useful quantities.
One method for obtaining n-hexenes is to convert 1-butene into 3-hexene by the well known metathesis reaction (also called a "dismutation" reaction) discussed by R. L. Banks in Chemtech, February 1986, p. 112. Ethylene is a co-product. The 3-hexene can be thermodynamically isomerized to an n-hexene mixture with acidic, basic or transition metal catalysts well known in the art. There are many references to the metathesis reaction; one reference, U.S. Pat. No. 3,595,920, issued July 21, 1971 to Alas et al., describes a silver-modified molybdenum oxide on alumina catalyst.
A known method for producing terminal olefins, such as 1-hexene, is to dehydrate a 2-alcohol, i.e., a compound of the formula ##STR1## where R is a hydrocarbyl group. For example, U.S. Pat. No. 3,283,027, issued Nov. 1, 1966 to Lundeen et al., discloses the dehydration of 2-alcohols to terminal olefins (also known as ".alpha.-olefins") using a catalyst which is a thorium, scandium, yttrium or rare earth oxide. While this dehydration reaction can produce an .alpha.-olefin and/or a 2-olefin, the Lundeen et al., product is said to be 90% or more .alpha.-olefin.
U.S. Pat. No. 3,600,455, issued Aug. 17, 1971 to Dean, discloses a process for producing the terminal olefin 4-methyl pentene-1 by dehydrating 4-methyl pentanol-1 or 4-methylpentanol-2 by passing it over an alkalized alumina catalyst.
U.S. Pat. No. 4,234,752, issued Nov. 18, 1980 to Wu et al., discloses the dehydration of C.sub.2-20 alcohols in the presence of gamma-alumina (which may be base-treated) employing an inert carrier gas to produce an olefin. The process is said to minimize isomerization which can convert desired products to undesired products. For example, according to Wu et al., 3-methyl-l-butanol can be dehydrated by this process to produce 3-methyl-1-butene having a 97.7 wt. % purity.
U.S. Pat. No. 4,490,567, issued Dec. 25, 1984 to Drake, discloses a process for the selective dehydration of 2-alcohols to .alpha.-olefins using a catalyst which is (1) at least one catalytic metal oxide on a low surface area aluminum oxide-containing support, or (2) a mixture of thorium oxide and cerium oxide on a base-treated aluminum oxide-containing support. Also described is a process for obtaining high purity 4-methyl-1-pentene by the dehydration of 4-methyl-2-pentanol followed by disproportionation with ethylene.
European Patent Specification Publication No. 0150832, published Nov. 2, 1988, discloses a process for preparing .alpha.-olefins by dehydrating 2-alcohols using a high purity (i.e., substantially free of silicon and titanium) zirconium oxide catalyst, and European Patent Specification Publication No. 0222356, published May 20, 1987, discloses the dehydration of 2-alcohols to .alpha.-olefins using a zirconia catalyst which has been treated with an alkaline solution.
Lundeen and Hoozer, "Selective Catalytic Dehydration. Thoria-Catalyzed Dehydration of Alcohols", J. Org, Chem., 32, pp. 3386-3389 (1967) discloses that the thoria-catalyzed dehydration of secondary 2-alcohols is selective for .alpha.-olefins, and that the amount of ketone by-product is low, and Davis, "Catalytic Conversion of Alcohols. 11. Influence of Preparation and Pretreatment on the Selectivity of Zirconia", Ind. Eng. Chem. Prod. Res. Dev., Vol. 18, No. 3, pp. 181-198 (1979) discloses that a zirconia catalyst is similar to thoria for both the dehydration and .alpha.-olefin selectivity in the conversion of 2-alcohols to olefins.
Other methods of preparing .alpha.-olefins are also known. For example, British Patent Specification No. 1,233,020, published May 26, 1971, discloses a method for making 4-methylpentene-l by subjecting a mixture of acetone and isobutyraldehyde to conditions under which acetone undergoes condensation both with itself to form diacetone alcohol and with isobutyraldehyde to form the acetone/isobutyraldehyde condensate methyl, 2-methyl 3-hydroxy butyl ketone, subjecting the mixed condensates to conditions under which they undergo dehydration to the corresponding olefinically unsaturated ketones, hydrogenating these ketones to saturated alcohols and dehydrating these saturated alcohols over alkalized alumina to form a mixture of 4-methylpentenes-1 and -2 and a mixture of methylhexenes.
A process for producing 1-hexene has now been discovered which uses 1-butene, which is abundant and relatively inexpensive, as the starting material.